Quaternary ammonium derivatives of n,n&#39;-substituted 4,4&#39; - bis(benzimidazol-2-yl)stilbenes

ABSTRACT

N,N&#39;&#39;-SUBSTITUTED 4,4&#39;&#39;-BIS(BENZIMIDAZOL-2-YL)STILBENES ARE INTERACTED WITH ALKYLATING AGENTS TO PRODUCE QUATERNARY AMMONIUM COMPOUNDS WHICH ARE PARTICULARLY USEFUL FOR COMMITANTLY DISINFECTING AND WHITENING OR BRIGHTENING TEXTILE MATERIALS.

United States Patent 3,583,984 QUATERNARY AMMONIUM DERIVATIVES FN,N'-SUBSTITUTED 4,4 BIS(BENZlMIDAZOL-2- YL)STILBENES 0 Nathan N.Crounse, Cincinnati, Ohio, asslgnor to Sterling Drug Inc., New York,N.Y. N0 Drawing. Filed Aug. 1, 1967, Ser. No. 657,515 Int. Cl. (307d49/38 US. Cl. 260-240 20 Claims ABSTRACT OF THE DISCLOSURE N,Nsubstituted 4,4'-bis(benzimidazol-Z-yl)stilbenes are interacted withalkylating agents to produce quaternary ammonium compounds which areparticularly useful for commitantly disinfecting and whitening orbrightening textile materials.

This invention relates to novel fluorescent compounds of thebenzimidazolylstilbene series useful as disinfecting agents and aswhitening and brightening agents, to their preparation and tosurface-active compositions containing them.

The present invention provides new fluorescent whitening and brighteningagents having antibacterial and antifungal properties which are usefulin the treatment of threads, sheets, films, filaments, textile fabrics,and the like, as well as in the manufacture of paper, varnishes, inks,coatings, and plastics. These new compounds are particularly welladapated to application to white and colored fabrics, since they aresubstantive even in low concentrations to a wide variety of natural andsynthetic fiber. They impart a desirable blue-white hue to white fibersand brighten colored fibers treated therewith, while at the same timeimparting an antibacterial and antifungal finish to the fibers.

The new compounds of this invention are quaternary ammonium salts of thebenzimidazolylstilbene series having the structure of Formula I shownbelow,

FORMULA I where R R R and R are hydrogen, lower alkyl having 1 to 4carbon atoms, lower alkoxy having 1 to 4 carbon atoms, or halo; Y and Yare lower alkyl having 1 to 6 carbon atoms, hydroxy-lower alkyl having 2to 6 carbon atoms, 2-hydroxy-3-sulfopropyl, hydroxy-oxaalkyl having 3 to15 carbon atoms, carboxy-lower alkyl having 2 to 6 carbon atoms,cyano-lower alkyl having 2 to 6 carbon atoms, phenyl-lower alkyl having7 to 11 carbon atoms, allyl or methallyl; Z and Z are lower alkyl having1 to 6 carbon atoms, hydroxy-lower alkyl having 2 to 6 carbon atoms,carboxy-lower alkyl having 2 to 6 carbon atoms, cyano-lower alkyl having2 to 6 carbon atoms, phenyllower alkyl having 7 to 11 carbon atoms,allyl, methallyl, or 3-halo-2-propenyl; and An is an anion.

When R R R and R represent lower alkyl having ing 1 to 4 carbon atoms,for example, there are included methyl, ethyl, n-propyl, isopropyl,n-butyl, isobutyl and the like. When Y Y Z and Z represent lower alkylhaving 1 to 6 carbon atoms, for example, there are included methyl,ethyl, n-propyl, isopropyl, n-butyl, isobutyl, namyl, n-hexyl and thelike. When R R R and R represent lower alkoxy having 1 to 4 carbonatoms, there are included for example, methoxy, ethoxy, n-butoxy, andthe like. When Y Y Z and Z represent lower alkyl havalkyl having 2 to 6carbon atoms, there are included for example, 2-hydroxyethyl,l-methyl-Z-hydroxyethyl and 2,3-dihydroxypropyl, and the like. When R RR and R represent halo, for example, there are included chlorobromo andfluoro.

When representing hydroxy-oxalkyl, having 3 to 15 carbon atoms, thegroups Y and Y include for example,2-hydroxy-3-(2,3-dihydroxypropoxy)propyl, 2-hydroXy-3- (2hydroxyethoxy)propyl, l methyl-2-(1-methyl-2-hydroxyethoxy)ethyl, 2-hydroxy 3-[2-(2-hydroxyethoxy) ethoxy] propyl, and the like.

When Y Y Z and Z represent carboxy-lower alkyl having 2 to 6 carbonatoms, there are included for example, carboxymethyl, 2-carboxyethyl,and 3-carboxypentyl. When Y Y Z and Z represent cyano-lower alkyl having2 to 6 carbon atoms, there are included for example, 2-cyanoethyl,3-cyanopropyl, and S-cyanopentyl.

The term phenyl-lower alkyl as used herein means a monovalenthydrocarbon radical consisting of phenyl bonded to one of the valencesof a divalent lower-alkylene radical having one to four carbon atoms asexemplified by, but not limited to methylene, 1,1-ethylene,1,2-ethylene, 1,3-propylene, 1,2-propylene, l,4-butylene, and the like.Thus, solely for illustration and without limitation, examples ofphenyl-lower alkyl are benzyl, l-phenylethyl, 2-phenylethyl,3-phenylpropyl, and the like.

The term anion, as used herein, means the anion of any salt-forminginorganic or organic acid. The choice of an anion is not critical in theoperation of the preparative processes nor is the identity of the aniona critical feature of the claimed products. Accordingly, by Way ofillustration and without limitation thereto, the anions can be forexample,

:bromoide, chloride, iodide, fluoride, nitrate, sulfate, phosphate,acetate, formate, p-toluenesulfonate, phenoxyacetate and the like. Whena pharmaceutical use is intended, it is preferred to employ anions ofpharmaceutically-acceptable salt-forming inorganic or organic acidssince the disinfecting properties of the quaternary ammonium compoundsof this invention make them applicable to human or animal use. Thus,such an acid is one whose anions are non-toxic and innocuous to theanmal organism in effective concentration of the quaternary ammoniumsalts so that beneficial properties inherent in the common structuralentity are not vitiated by side-effects ascribable to the anion.

In general, the compounds of the above structure are high-melting whiteor yellow solids. They are generally soluble in water and thelower-alkanols and are insoluble in hydrocarbons, halogenatedhydrocarbons, ketones, and ethers. They are moderately soluble inN,N-dimethylformamide and dimethyl sulfoxide and some of them aresoluble in acetic acid.

When the compounds of the present invention are dissolved in aqueousmedia, they fluoresce blue-white under ultraviolet light and show a widerange of absorption in the ultraviolet region. They are substantive to awide variety of natural and synthetic fibers, for example, cotton,cellulose acetate, viscose rayon, nylon, silk, and polyacrylonitrile(Orlon-Du Font) and are absorbed by such fibers even from very lowconcentrations in aqueous solutions. My new compounds have relativelyhigh stability to sunlight, synthetic detergents, andchlorine-containing bleaching agents.

The above-described properties of my new compounds make them especiallyvaluable as whitening and brightening agents in treating white andcolored fabrics to neutralize the yellowness in white textiles or toenhance the brilliance of colored textiles. In such utilization, therelatively high resistance of my compounds to chlorine bleaching and tolight are distinct advantages, since many of the previously knownwhitening and brightening agents of the stilbene series have had astheir chief drawbacks a lack of resistance to chlorine-containingbleaching agents and ease of decomposition under influence of light.

A further important advantage of the preferred species of this inventionlies in the fact that on repeated applications to white fabrics, therebybuilding up the amount of the whitening agent on the fibers, the fabricsremain bluish white and do not develop undesirable discoloration, forexample a red or gray color, such as is produced by many of of the knownoptical bleaching agents when they are applied repeatedly, as forinstance in successive launderings.

The compounds described and claimed herein are of unique value, becausein addition to their usefulness as whitening agents, they also havebiostatic properties and are useful as antibacterial and antifungalagents. Thus, when tested by standard serial dilution procedures, thesecompounds were found to have bactericidal, bacteriostatic, fungicidal,and fungistatic activity in vitro. More specifically the quaternaryammonium compounds of this invention have been found to possessantibacterial activity toward Staphylococcus aureus 209, Salmonellatyphosa Hopkins, Bacterium ammoniogenes, Clostridz'um welchii M, andPseudomonas aeruginosa 211. They also posses antifungal activity towardTrichophyton mentagrophytes, Aspergillus niger and Monz'lia albicans.The substantivity of the compounds of this invention to a variety oftextiles together with the above-mentioned activities provide a means ofimparting long-lasting antibacterial and antifungal properties as wellas brightening or whitening effects to fibrous materials. For example,it has now been found that textile materials, which undergo successivelaunderings wherein the compounds of this invention are employed asmentioned hereinbefore, have the property of markedly inhibiting thegrowth of bacteria and of destroying existing bacteria.

The treatment of textile fabrics with these compounds is readily carriedout by conventional procedures. For example, an aqueous solutioncontaining about 0.0001 to 0.5 by weight of the compound is applied tothe fabric, which absorbs the fluorescent compound and is whitened orbrightened beneficially thereby. This application of the compound can beconveniently carried out in conjunction with a rinsing or washingoperation.

A convenient mode of using and marketing the compounds of this inventionis by incorporating them into solid or liquid detergets in anappropriate concentration, for example 0.02 to 0.5% by weight. Nonionicdetergents are preferred for this purpose. However, anionic and cationicdetergents can be employed without adversely affecting the germicidal orwhitening and brightening prop- 4 erties of the quaternarybenzimidazolium compounds of this invention.

The compounds of my invention can be prepared by employing as startingmaterials appropriate 4,4'-bis (benzimidaZol-2-yl)stilbenes. In general,I have found that it is convenient to start with the compounds havingthe structural formula FORMULA II wherein R R R and R have thepreviously-given meanings.

The N,N-unsubstituted compounds (Formula H) react readily withalkylating agents to yield symmetrical or unsymmetrical N,N-di(alkyl orsubstituted alkyl) derivatives. The substituting groups are alkyl orsubstituted alkyl radicals of the type hereinbefore defined as Y and Yin Formula I. The alkylating reaction is readily carried out asdescribed in US. Pat. 2,838,504, viz., by heating a 4,4--bis(benzimidazo-2-yl)stilbene with the appropriate .alkylating agent.The N,N'-disubstituted intermediates having the structural formulaFORMULA III wherein Y and Y have the same meanings given hereinbefore,are then further caused to react with the same or different alkylatingagents to produce the quaternary benzimidazolium salt compounds of myinvention. The compounds of Formula I, wherein Y =Y =Z =Z can beprepared without isolation of the N,N'-disubstituted intermediate byreacting the appropriate N,N'-unsubstituted compound of Formula II withan excess of alkylating agent over the stoichiometrically-required fourmolecular equivalents.

The 4,4'-bis (benzimidazol-Z-yl)stilbenes of Formula II used as startingmaterials in this invention are known in the prior art and are describedwith their preparation in US. Pat. 2,838,504. They are prepared bycyclization of a bis(ortho-aminoanilide) of a 4,4'-stilbene-dicarboxylicacid by heating it under acidic conditions. For example, the followingcompounds of Formula II are useful starting materials for preparing thequaternary ammonium salt compounds of my invention. (As will beappreciated, the tautomerism of these products affords in many casesalternative choices of designation for a single substance; these choicesare indicated hereinbelow, where appropriate, in accordance withconventional nomenclature requirements) 4,4-bis (benzimidazol-Z-yl)stilbene; 4,4-bis [4 (or 7) -methoxybenzimidazol-Z-yl1stilbene; 4,4-bis[4 (or 7 -ethoxybenzimidazol-2-yl] stilbene; 4,4-bis[ (or 6-isopropoxybenzimidazol-2-yl1stilbene; 4,4'-bis 5,6-dimethoxybenzimidazol-Z-yl) stilbene 4,4'-bis( 5,6-dibutoxybenzimidazol-2-yl stilbene; 4,4'-bis [4,5 ,7 (or 4,6,7-trimethoxybenzimidazol-Z-yl] stilbene; 4,4'-bis [4 (or 7-methylbenzimidazol-2-yl] stilbene; 4,4'-bis 5 (or 6-tert-butylbenzimidazoLZ-yl] stilbene; 4,4-bis 5 ,6-dimethylbenzimidazol-Z-yl stilbene; 4,4-bis (4,5,6,7-tetramethylbenzimidazol-Z-yl stilbene; 4,4'-bis [5 (or6)-ethylbenzimidazol-2-yl] stilbene; 4,4-bis 5 (or 6-chlorobenzimidazol-2-yl] stilbene 4,4-bis [5 (or 6-fluorobenzimidazol-2-yl] stilbene; 4,4'-bis [4, 6 (or 5,7-dibromobenzimidazol-2-yl] stilbene; 4,4-bis 4,5 ,6 or 5, 6,7)-trichlorobenzimidazol-2-yl] stilbene; 4,4-bis 6-methoxy-5-fiuoro (or5-methoxy-6-fluoro) benzimidazol-Lyl] stilbene; 4,4'-bis[4-bromo-6,7-methylenedioxy (or 7-bromo-4,5- methylenedioxybenzimidazol-Z-yl] stilbene; and 4,4'-bis 5-methoxy- 6-methyl (or 5-methyl-6-methoxy) benzimidazol-Z-yl] stilbene.

The alkylating agents useful in this conversion are well known in theprior art and are esters of strong organic and inorganic acids havingthe formula Z-An, where Z is a member of the class consisting of loweralkyl having 1 to 6 carbon atoms, hydroxy-lower alkyl having 2 to 6carbon atoms, 2-hydroxy-3-sulfopropyl, hydroxy-oxaalkyl having 3 tocarbon atoms, carboxy-lo wer alkyl having 3 to 6 carbon atoms,cyano-lower alkyl having 2 to 6 carbon atoms, and phenyl-lower alkylhaving 7 to 11 carbon atoms; and An is an anion as hereinbefore defined.Illusnative of these esters are: methyl sulfate, ethyl sulfate; methylp-toluenesulfonate; lower alkyl halides, for example methyl chloride,ethyl bromide, butyl chloride, and hexyl chloride; phenyl-lower alkylhalides, for example benzyl chloride, p-methoxybenzyl chloride,o-chlorobenzyl chloride, 2-chloro-4-methoxybenzyl bromide, and benzylbromide; allyl and methallyl halides, for example allylchloride andmethallyl bromide; carboxy-lower alkyl halides, for example2-carboxyethyl chloride and carboxymethyl bromide; cyano-lowver alkylhalides, such as 2- cyanoethyl chloride; hydroxy-lo wer alkyl halides,such as 2,3-dihydroxypropyl chloride (or glycerol alpha-chlorohydrin),ethylene chlorohydrin, ethylene bromohydrin, isobutylene chlorohydrin;2-hydroxy-3-sulfopropyl chloride or bromide; hydroxy-oxaalkyl halides,for example 2-hydr0xy-3-(2-hydroxyethoxy)propyl chloride,2-hydroxy-3-(2,3-dihydroxypropoxy)propyl chloride and 2- hydroxy-3-[2-(2hydroxyethoxy)ethoxy1propyl chloride. Also useful as alkylating agentsare 1,2-lower alkylene oxides having 2 to 6 carbon atoms, for example,ethylene oxide, propylene oxide, glycidol, and epichlorohydrin; andacrylonitrile and methacrylonitrile.

The substitution of simple moieties in the benzene rings of the startingmaterials used in the processes above-described, i.e. in thephenyl-lower alkyl alkylating agents and in the stilbene moiety of thecompounds of Formula II, for example, halo (viz. chloro, bromo andfluoro), alkyl, lower alkoxy, lower alkylsulfonyl, lower alkylsulfinyl,nitro, and trifiuoromethyl, does not interfere with the operability ofthe process, and the resulting quaternary benzimidazolium compoundscorrespondingly substituted in said benzene rings thereof have the sameutility as, and are the full equivalents of, the compounds hereinclaimed.

The chemical structures of the compounds of the invention wereestablished by their mode of synthesis and are corroborated by thecorrespondence between calculated values for the elements and valuesfound by chemical analysis and by concordant spectral properties.

The following procedures and examples will further illustrate specificembodiments of the invention without the latter being limited thereto.

PRODUCTS AND PROCESSES Example 1 To a stirred solution of 24.6 g. (0.05mole) of 4,4- bis(1-allylbenzimidazol-2-yl)stilbene in 137.5 ml. of 2-methoxyethanol at 105 C. there was added dropwise, over 10 a period ofthirty minutes, 31.2 g. (0.22 mole) of methyl iodide. The mixture wasstirred at a temperature between 95 and 105 C. for two hours and thenthe solvent removed in vacuo. Acetone was added to the residue. Thesolid was collected by filtration and washed with fresh a acetone.Recrystallization from boiling methanol gave 4,4'-stilbenebis(l-allyl-3-methyl 2 benzimidazolium iodide), a yellow powder, M.P. 296297C. (dec.) (corr.). (corr.).

Example 2 A stirred mixture of 21.0 g. (0.043 mole) of 4,4-bis(l-allylbenzimidazol-Z-yl)stilbene and 118 ml. of 2- ethoxyethanol'was heated to reflux. To the solution thus formed there was added at105 C. dropwise over a period of forty-five minutes, 140 g. (1.02 mole)of n-butyl bromide. The mixture was then stirred and heated at atemperature between 95 and 105 C. for a total of twentyeight hours withthe addition as needed of small quantities of anhydrous sodium carbonate(for neutralizing acid resulting from solvolysis). The reaction mixturewas cooled and the solid that separated was filtered 01f, washed withfresh 2-ethoxyethanol, and then with acetone. The solid wasrecrystallized from boiling n-butanol to obtain 4,4'-stilbenebis(1-allyl-3 -n-butyl-2-benzimidazolium bro- 35 nzide) 31s a beige-coloredsolid, M.P. 272.0-273.2 C. (dec.)

corr.

Example 3 hydrous ethyl alcohol was a yellow powder, M.P. 284 C (dec.)(corr.).

Example 4 To a stirred solution of 24.6 g. (0.05 mole) of 4,4'-bisl-allylbenzimidazol-Z-yl)stilbene in 137 ml. of Z-ethoxyethanol at 105C. there was added dropwise over a period of ten minutes 12.2 g. (0.11mole) of 1,3-dichloropropene. Stirring and heating at a temperaturebetween 95 and 100 C. were continued for a total of 57 hours duringwhich period there was added an additional 24.0 g. (0.216 mole) of1,3-dichloropr0pene and small quantities of 35% aqueous sodium hydroxidesolution as needed (for neutralizing acid resulting from solvolysis).The solvent was evaporated in vacuo and acetone was added to theresidue. The solid was collected, washed with fresh acetone andrecrystallized from benzene/n-butyl alcohol to obtain 4,4-stilbenebis[1-allyl-3-(3-chloro-2-propeny1) 2 benzimidazolium chloride],and off-white solid, M.P. 252253 C. (dec.).

Example 5 A solution of 24.6 g. (0.05 mole) of4,4'-bis(1-allylbenzimidazol-Z-yl)stilbene in 137.5 ml. ofZ-methoxyethanol was stirred and heated at 105 C. while during a periodof fifteen minutes a solution of 35.4 g. (0.22 mole) of 4-chlorobenzylchloride in 25 ml. of Z-methoxyetha- 1101 was added dropwise. Stirringand heating at a temperature between and C. were continued for threehours. The solvent was evaporated under reduced pressure, and acetonewas added to the residue. The solid that separated was collected, washedwith fresh acetone and then recrystallized from 2-methoxyethanol/acetonewith the aid of decolorizing charcoal to obtain 4,4'-stilbenebis[1-allyl-3- (4-chlorobenzyl -2-benzimidazolium chloride], a pale yellowsolid, M.P. 205.5 (froth)-206.5 C. (dec.) (corn).

Example 6 To a stirred solution of 14.8 g. (0.03 mole) of 4,4-bis(1-allylhenzimidazol 2 yl)stilbene in 82.5 ml. of 2- methoxyethanolheated at a temperature between 95 and 100 C. there was added over aperiod of twenty minutes, 22.8 g. (0.106 mole) of powdered 4-nitrobenzylbromide. The mixture was stirred and maintained at a temperature between95 and 100 C. for a period of one and threequarter hours. Approximatelythree-fourths of the solvent was evaporated under reduced pressure andacetone was added to the residue. The suspension was chilled at 5 C. forthirty minutes and the solid that separated was collected, washed withfresh acetone and dried at 75 C. to obtain 4,4stilbenebis[1-allyl-3-(4-nitrobenzyl)-2- benzimidazolium bromide], ayellow solid, M.P. 249.2- 262 C. (dec.) (corn).

Example 7 Employing the procedure of Example 5 above, 49.2 g. (0.1 mole)of 4,4-bis(1-allylbenzimidazol-2-yl)stilbene in 275 ml. of2-methoxyethanol was treated with a solution of 43.0 g. (0.22 mole) ofmixed (2,5 isomer=50%; 2,4 isomer=37%; 3,4 isomer=13% dichlorobenzylchloride in 25 ml of Z-methoxyethanol to obtain4,4-stilbenebis[l-allyl-3- (dichlorobenzyl) 2 benzimidazolium chloride],a yellow solid.

Example 8 Following the procedure of Example 1 hereinabove, 25.0 g.(0.051 mole) of 4,4'-bis(l-allylbenzimidazol-Z- yl)stilbene and 29.9 g.(0.1 mole) of 2,3,4,5,6-pentachlorobenzyl chloride were interacted in125 ml. of 2- methoxyethanol. There was thus obtained 4,4-stilbenebis[1-allyl-3-(2,3,4,5,6-pentachlorobenzyl) 2 benzimidazolium chloride], ayellow solid.

Example 9 Using the procedure of Example 5 hereinabove, but substituting4-dodecylbenzyl chloride for 4-chlorobenzy1 chloride used in thatexample, there was obtained 4,4- sti1benebis[1-ally1-3-(4-dodecylbenzyl)2 benzimidazolium chloride], a yellow solid, M.P. 103-105 C.

Example 10 (A) Alkylation of 4,4'-bis(benzimidazol-2-yl)stilbene withethylene oxide.A mixture of 550 g. (1.33 moles) of4,4-bis(benzimidazol-Z-yl)stilbene, 2,68 liters of 95% ethanol and 174g. (4.35 moles) of sodium hydroxide pellets was heated at 76-86 C. and540 g. of ethylene oxide was passed into the resulting solution over aperiod of six hours. At this point, 141 g. (2.35 moles) of glacialacetic acid was added to the solution dropwise during a period offifteen minutes. During a period of four hours an additional 181 g. ofethylene oxide was passed into the solution. The reaction mixture wasthen poured in a thin stream into a rapidly agitated solution of 196.5g. of sodium chloride in 19.65 liters of water at 30 C. The mixture wasstirred for thirty minutes and the precipitated solid was collected byfiltration. The solid was washed with fresh water until free of alkali.There was thus obtained after drying to constant weight 664.5 g. ofproduct which was chiefly a mixture of4,4-bis[1-(2-hydroxyethyl)benzimidazol 2 yl]stilbene,4-[1-(2-hydroxyethyl) benzimidazol-Z-yl] 4 {l-[2-(2-hydroxyethoxy)ethyl]benzimidazol 2 yl}stilbene and4,4'-bis{1-[2-hydroxyethoxy)ethyl]benzimidazol-2-yl}stilbene.

(B) A solution of 45.0 g. of the mixture of hydroxyethylated productsobtained as described above, and 225 ml. of 2-methoxyethanol was heatedat reflux during a period of fifteen minutes. The temperature waslowered to 75 C. and during twenty-five minutes a solution of 19.0 g.(0.157 mole) of allyl bromide in 19.0 ml. of 2-methoxyethanol was addeddropwise. The mixture was refluxed for two and one-half hours and thenconcentrated by distilling off a portion of the solvent. To the cooledresidue there was added 200 ml. of acetone and the solid that separatedwas collected. The solid was dissolved in ml. of boiling 95 ethanol andthe solution chilled. A solid separated and was removed by filtration.The alcohol filtrate was then poured into 1 liter of acetone at 810 C.and the mixture further diluted with 500 ml. of acetone. The mixture wasstored in a refrigerator overnight and the solid that separated wascolled by filtration, washed with 200 ml. of acetone, and dried toconstant weight to obtain chiefly4,4'-sti1benebis{l[2-(2-hydroxyethoxy)ethyl] 3 allyl-2-benzimidazoliumbromide}, melting at 140-145 C. with decomposition.

Example 11 Following the procedure described in Example 10 hereinabove,but substituting 24 g. (0.149 mole) of 4-ch1orobenzyl chloride for the19 g. of allyl bromide used in that example, there was obtained chiefly4,4'-sti1benebis {1-[2(2-hydroxyethoxy)ethyl] 3 (4 chlorobenzyl)2-benzimidazolium chloride}, a tan solid, melting at C. withdecomposition.

Example 12 With stirring, 27.5 g. of the mixture of hydroxyethylatedproducts obtained as described above was dissolved in 275 ml. ofrefluxing 2-methoxyethanol. The temperature of the solution was loweredto 75 C. and 19.5 g. (0.10 mole) of 3,4-dichlorobenzyl chloride wasadded dropwise during fifteen minutes. Reflux was reestablished and wascontinued for four hours. The mixture was cooled in a refrigeratorovernight. Then 200 ml. of diethyl ether was added to the stirredmixture. A solid separated and was collected by filtration. The solidwas washed with fresh ether and dried in a vacuum desiccator to obtainas a yellow solid, a mixture comprised chiefly of 4,4-stilbenebis[1 (2hydroxyethyl)-3-(3,4-dichlorobenzyl)-2-benzimidazolium chloride] and4-[1-(2-hydroxyethyl)benzimidazol 2yl]-4-{1-[2-(2-hydroxyethoxy)ethyl]benzimidazol 2 yl}stilbene N ,Nbis(3,4-dichlorobenzy1 chloride).

Example 13 Using the procedure of Example 12 hereinabove, butsubstituting 2,4-dichlorobenzyl chloride for 3,4-dichlorobenzyl chlorideused in that example, there was obtained as a yellow solid a mixturecomprised chiefly of 4,4- stilbenebis[1 (2hydroxyethyl)-3-(2,4-dichlorobenzyl)- 2-benzimidazoliurn chloride] and4-[1-(2-hydroxyethyl) benzimidazol 2 yl]-4-{1-[2-(2 hydroxyethoxy)ethyl]benzimidazol-2-yl}stilbene N ,N '-bis(2,4-dichlorobenzyl chloride).

Example 14 Following the procedure described in Example 12 hereinabove,but substituting 2,3,4,5,6-pentachlorobenzyl chloride for the3,4-dichlorobenzyl chloride used in that example, there was obtained asa mustard-colored powder a mixture comprised chiefly of4,4-stilbenebis[3-(2,3,4, 5,6-pentachlorobenzyl) 1 (2hydroxyethyl)-2-benzimidazolium chloride] and 4 [1(2-hydroxyethyl)benzimidazol 2yl]-4-{1-[2-(2-hydroxyethoxy)ethyl]benzimidazol 2 yl}stilbene N ,N'bis(2,3,4,5,6-pentachlorobenzyl chloride).

Example 15 (A) Alkylation of 4,4-bis(benzimidazol-Z-yl)stilbene withpropylene oxide.A mixture of 61.5 g. (0.15 mole) of4,4'-bis(benzimidazol-Z-yl)stilbene, 321 ml. of ninetyfive percent ethylalcohol, and 47.5 g. of a 50% aqueous solution of sodium hydroxide washeated at reflux for thirty minutes to effect solution. The temperaturewas then lowered to 75 C. and during a period of four hours a total of102 g. (1.76 moles) of propylene oxide was added in small portions.Heating at reflux was continued for a period of several hours and themixture was then cooled. A solid had separated. The mixture was filteredand the solid thus collected was washed in a solution of 160 ml. ofethyl alcohol and 6.7 ml. of a 50% aqueous solution of sodium hydroxide.The solid was then further washed with ethyl alcohol and dried toconstant weight in a vacuum oven. There was thus obtained 58.7 g. ofproduct as a yellow-gray powder which was chiefly a mixture of 4,4-bis1-( 1-methyl-2-hydroxyethyl)benzimidazol- 2-yl]stilbene and4-[l-(I-methyl-Z-hydroxyethyl)benzimidazol 2 yl]-4-{l-[l-methyl 2(2,3-dihydroxypropoxy ethyl] benzimidazol-Z-yl}stilbene.

(B) With stirring, 25.4 g. of the mixture of hydroxypropylated productsobtained as described above, and 125 ml. of Z-methoxyethanol were heatedtogether at 80 C. while during a period of fifteen minutes a solution of17.0 g. (0.105 mole) of 4-chlorobenzyl chloride in 17.0 ml. of2-methoxyethanol was added dropwise. The mixture was refluxed forforty-eight hours and after cooling, filtered to remove a small amountof undissolved solid. The filtrate was diluted with 1.5 liters ofdiethyl ether causing a solid to separate. The mixture was set asideovernight, and the solid was collected by filtration, washed withdiethyl ether and dried to obtain chiefly 4-[1-(1- methyl 2hydroxyethyl)benzimidazol 2-yl]4-{1-[1- methyl 2(2,3-dihydroxypropoxy)ethyl]benzimidazol 2-yl}stilbene N ,N-bis(4-chlorobenzyl chloride).

Example 16 A mixture of 10.5 g. (0.025 mole) of4,4'-bis(benzimidazol-2-yl)stilbene and 110 g. (0.86 mole) of benzylchloride was stirred and heated at reflux for a total of twenty-onehours. The mixture was filtered, and the collected solid was washed withbenzene, and dried in a vacuum oven. Recrystallization of the solid fromboiling 95% ethanol with the aid of decolorizing charcoal gave4,4'stilbenebis( 1,3-dibenzyl-2-benzimidazoliurn chloride) as thetrihydrate, an off-white solid, M.P. 254.0-260.3 C. (dec.) (corn).

Example 17 Forty-five grams of the mixture of hydroxyethylated productsobtained as described above (Example A) was dissolved in 200 ml. ofrefluxing 2-methoxyethanol. The temperature of the solution was loweredto 100 C. and 6.7 g. (0.038 mole) of a,o-dichloro-p-xylene was addedover a period of five minutes. Reflux was reestablished and wascontinued for four hours. The mixture was set aside overnight at roomtemperature, and then was filtered to remove a small amount of insolublematerial. The filtrate was diluted with 1.4 liters of diethyl ethercausing a gum to separate. The ether was decanted from the gum and 300ml. of fresh diethyl ether was added to the gum. Manual working of thegum produced a powdery solid which was collected, washed with freshdiethyl ether and dried to obtain a mustard-colored powder having thestructural formula:

and chemically named as a,a'-bis((2-4'-{l-[2-(2-hydroxyethoxy)et'hyl]benzimidazol 2 yl}stilbenZyl-4 -1- [2(2 hydroxyethoxy)ethyl] 3-benzimidazolium) )-p xylene dichloride.

When the procedures of Examples 1, 2, 3, 4, 5, 6, 10B, 12, 15B, 16, or17 are followed in reacting the appropriate N,N'-substituted orunsubstituted 4,4 bis- (benzimidazol 2 yl)stilbcne with the appropriatealkylating agent as defined hereinbefore there are obtained:

' 4-[1-methyl-(5 or 6)-chlorobenzimidazol-2-yl]-4- l-ethyl- S or 6-chlorobenZimidazol-2-yl stilbene N N -bis(methy1sulfate)4,4-stilbenebis[ 1-(2-hydroxyethyl)-3-(4-methylbenzyl)5,6-dimethyl-2-benzimidazolium chloride];

4,4-stilbenebis 1- [2- 2-hydroxyethoxy ethyl] -3- 2,5

dichlorobenzyl)-5 (or 6)-tert-butyl-2-benzimidazolium chloride};

4,4'-stilbenebis[1-(2,4-dichlorobenzyl)-3-(4-dodecylbenzyl -5 (or 6)-chloro-2-benzimidazolium chloride];

4,4'-stilbenebis 1- 3-methylbenzyl -3-( 3 -bromopropenyl)-5 (or6)-chloro-2-benzimidazolium bromide];

4,4'-stilbenebis[1-(2,3-dihydroxypropyl)-3-n-butyl- 2-benzimidazoliumchloride];

4,4stilb enebisl 1- 2-carboxyethyl -3-methallyl-2- benzimidazoliumchloride 4,4'-stilbenebis[1-(2hydroxyethyl)-3 -methal1yl-5,6-

dimethyl-2-benzimidazolium chloride];

4,4'-stilbenebis[1-(2-hydroxy-3-sulfopropyl)-3-phenethyl-2-benzimidazolium chloride];

4,4-stilbenebis{1-[2-(2-hydroxyethoxy)ethyl] -3-benzyl- 5 (or6)-tert-buty1-2-benzimidazolium chloride};

4,4'-stilbenebis[1-(2-cyanoethyl)-3-carboxymethyl- 2-benzimidazoliumchloride 4,4'-stilbenebis{ 1-[2-hydroxy-3-(2,3-dihydroxypropoxy) propyl]-3-methy1-2-benzimidazolium iodide};

4,4'-stilbenebis{ 1- 2-hydroxy-3-[2-(2-hydroxyethoxy) ethoxy] propyl-3-benzyl-2-benzimidazolium chloride};

4,4'-stilbenebis[ 1-( 2-carboxyethyl -3 4-fluorobenzyl 2-benzimidazoliumchloride];

4,4'-stilbenebis( 1-allyl-3-n-butyl-4,5,6,7-tetramethyl-2-benzimidazolium bromide);

4,4-stilbenebis[ 1- (2-cyanoethyl -3-benzyl-6-methoxy- 5-fluoro(or5-methoxy-6-fiuoro -2-benzimidazolium bromide] 4-1-carboxymethylbenzimidazol-2-yl -4'-( l-methylbenzimidazol-Z-yl)stilbene N N -bis(4-bromobenzyl bromide);

4,4'-stilbenebis 1- (2-cyanoethy1) -3-isopropyl-2- benzimidazoliumbromide];

4-[ l- (2-carboxyethyl)benzimidazol-2-yl] -4'-(l-methylbenzimidazol-Z-yl)stilbene N N '-bis (methallyl chloride)4,4-stilbenebis[1-(2-chlorobenzyl)-3-(2-hydroxy-2- sulfopropyl)-2-benzimidazolium chloride]; and

4-( l-methylbenzimidazol-2-yl)-4-{1-[2-hydroxy-3-(2-hydroxyethoxy)propyl] benzimidazol-Z-yl}stilbene N N -bis3-methylbenzyl bromide).

As will be evident to the skilled chemist, the mixtures obtained in thealkylation of 4,4'-bis(benzimidazol-2-yl)stilbene with ethylene oxide orwith propylene oxide can be separated from one another by physicalmeans, for example, recrystallization, to give the individualhydroxyethyl or hydroxypropylated 4,4'-bis(benzimidazol-2-yl)stilbene inessentially pure form. From their intermediates, the individualquaternary benzimidazolium compounds can be prepared in essentially pureform by the methods disclosed herein. However, since all of the finalproducts thus obtained are antibacterial and antifungal whitening andbrightening agents, for many purposes there is no particular advantagein separating them and it is ordinarily preferred to use the mixtures ofthe quaternary benzimidazolium salts obtained as described in Examples10B through 15B and 17 as such, Without purification.

Following are representative results obtained when the compoundsprepared in accordance with the foregoing examples of the instantinvention were tested in vitro by standard serial dilution proceduresfor bacteriostatic (Bs), bactericidal (Bc), fungistatic (Fs), andfungicidal (Fc) properties; these results are expressed as minimumconcentration of the test compound, in parts per million, required forno growth of the test organism. For example, in antibacterial tests,using Staphylococcus aureus 209, Salmonella typhosa Hopkins, Clostridiumwelchii M, and Pseudomonas aerugimosa 211, the results obtained were asfollows:

the desired quantity of an aqueous solution of an anionic or non-ionicdetergent or of a laundry additive. The resulting fluorescentdispersions were used to dye white and colored natural synthetic fibers.All of the quaternary ammonium benzimidazolylstilbene products of theabove examples were found to be substantive even from lowconcentrations, e.g. 0.0001%, in these aqueous media to white andcolored fabrics of cotton, cellulose acetate, nylon, viscose rayon,polyacrylonitrile (Orlon-Du Pont) and silk, thereby imparting ablue-white hue to the white fabrics and brightening the colored fabrics,while at the same time imparting an antibacterial and antifungal finishto the fabrics. Moreover, these products all had high stability to lightas determined by exposure tests. In the solutions in detergents theproducts were substantially unaffected by a concentration of sodiumhypochlorite of 0.2% by weight. The new products of this invention werethus found to be especially useful as whitening and brightening agentsto be used in conjunction with the laundering of white and coloredfabrics.

A preferred mode of using and marketing the compounds of this inventionis by incorporating them into solid or liquid detergents in aconcentration of 0.02 to 0.5 percent of the whitening and brighteningagent by weight. Although a concentration of less than 0.02 percentimparts an antibacterial and antifungal finish to the fabrics, thewhitening and brightening elfect at such concentrations is inadequateunder ordinary laundering procedures. Moreover, a concentration higherthan 0.5 percent is uneconomical and unnecessary since no increasedWhitening and brightening is effected at such higher concentrations.

The detergents which are employed are prefer-ably water-solublesynthetic organic anionic and non-ionic detergents; these are of coursewell-known classes of substances. Thus, for example there can be usedorganic sulfates and sulfonates, for instance sodium lauryl sulfateCompound Staph. aurcus Sal. lyphosa OZ. welchii P8. aerug. of ExampleNo. Bs Be 135 B B B0 Bs Be In antifungal tests, using Trichophytonmentagrophytes, Aspergillus niger, and Monilia albicans as the testorganisms, the following results were obtained:

T. mentag. As. m'ger Mon. alb. Compound of Example No. Fs F0 F5 Fe Fs FeCompositions When the quaternary ammonium benzimidazolylstilbenesdescribed in the foregoing examples were dispersed in aqueous media, theproducts in each instance fluoresced blue-white under ultraviolet lightand showed a wide range of absorption in the ultraviolet region. Each ofthe products of these examples was dissolved in a suitable solvent, forinstance, ethanol, Z-methOxyethanoI or N,N-dimethylformamide, dependingon the solubility characteristics of the particular product, and thesolution thus obtained was poured with vigorous stirring into A solutionof 0.15 g. of the product of Example 3 in ml. of N,N-dimethylformamidewas diluted with water to 250 ml. A Launder-O-Meter (a standardlaboratory washing machine of the American Association of TextileChemists and Colorists, manufactured by Atlas Electric Devices, Chicago,Ill. and described in the Technical Manual and Year Book of theAssociation, Howes Publishing Co., Inc., New York, N.Y., volume XXVIII,

1952, pages 82-83) jar was charged with 2.0 ml. of the brightenersolution and 53.5 ml. of a 0.4% solution of an alkyl aryl sulfonatedetergent which initially contained no brightening agent. Then 51.5 ml.of tap water and two 5.0 gram swatches of cotton cloth were added to thejar. The Launder-O-Meter was run for twenty minutes at 120 F. The clothwas removed, rinsed for two minutes in cold running tap water and thenironed dry. The fabric thus treated had a brightness greater than thatof the untreated sample. After laundering the fabric a total of sixtimes according to this procedure, the fluorescence as measured by thefiuorimeter, increased to approximately 300 percent of the fluorescentstrength found on control cloths washed with the detergent solutiondescribed above but containing no quaternary ammonium brightening agent.

When the cloth samples thus treated with the quaternary ammoniumfluorescent compounds of this invention were innoculated with a knownnumber of bacteria and were then incubated at 37 C. for 18 to 24 hours,it was found that the viable Staphylococcus aureus 209 had been reducedby 97.5 percent as calculated by comparison with the control cloths.

Example 19 Following the procedure described in Example 18 hereinabovebut substituting a non-ionic polyoxyethylene ether detergent initiallycontaining no brightener for the anionic detergent used in that exampleand adding 0.4 ml. of a 5.25 percent aqueous solution of sodiumhypochlorite, the fluorescence of the cotton samples after sixlaunderings as measured by the fiuorimeter was increased toapproximately 400 percent of the fluorescent strength found on controlcloths washed in the same detergent mixture but containing no quaternaryammonium brightener.

Moreover, when a known number of bacteria were placed on the cottonsamples laundered as described above, and the number of viable bacteriadetermined after incubation at 37 C. for 18 to 24 hours, it was foundthat a 99 percent and a 94 percent reduction of Staphylococcus aureus209 and Escherichia coli respectively had been effected as calculated bycomparison with the control cloths.

Example 20 A 3.5% solution of di-(hydrogenated tallow)dimethyl ammoniumchloride was prepared by adding water heated to 75 C. to the moltenmaterial with vigorous agitation. The emulsion thus formed was heated ona steam bath for a period of fifteen minutes to effect completesolution. Then 0.25 ml. of the solution, 20 mg. of the product ofExample dissolved in 2.0 ml. of ethanol, and distilled water to make atotal volume of 200 ml. were added to a Launder-O-Meter jar. The samplecontainers were then placed in the water bath of the Launder-Q-Meter androtated for ten minutes at 100 F. Ten grams of unbleached cotton wasthen added to each jar. The jars were returned to the water bath androtated for two minutes at 100 F. The swatch was removed from thecontainer, the excess solution was squeezed out and the cloth dried in adrum drier. This procedure imparted a blue-white fluorescence to thefabric.

The sample thus treated was evaluated for antibacterial effectiveness bythe Agar Plate Method developed by the American Association of TextileChemists and Colorists. When a 23 mm. diameter disc of the treatedsample was placed on an agar plate that had previously been innoculatedwith Staphylococcus aureus 209 and then the entire incubated at 37 C.for 18 to 24 hours, a clear zone of inhibition 25 mm. in diameter wasproduced. Discs of control cloth, treated in the solution describedabove but containing no quarternary ammonium brightening agent, showedno zone of inhibition when tested in the same manner.

14 Example 21 A Launder-O-Meter jar was charged with 53.5 ml. of a 0.4%aqueous solution of a non-ionic detergent (initially containing nobrightener), 51.5 ml. of a 0.6% aqueous solution of a laundry additive,2.0 ml. of a 0.04% aqueous solution of the product of Example 3hereinabove and two five gram cotton swatches. The laundry additive usedin this example was comprised of 98.4% of sodium tetraboratedecahydrate, 0.4% of dodecyl benzene sulfonate and 1.2% of inertingredient. No brightening agent was present initially in the laundryadditive or the nonionic detergent. The Launder-O-Meter was run fortwenty minutes at 120 F.; the cloths were removed, washed for twominutes in cold, running tap water and then ironed dry. After a total ofsix launderings according to this procedure, the fluorescence increasedto approximately 240 percent of the fluorescent strength found on clothwashed in the same solution but containing no quarternary ammoniumbrightener.

The cloth samples thus treated were innoculated with a known number ofbacteria and were then incubated at 37 C. for 18 to 24 hours. It wasfound that viable Staphylococcus aureus 209 had been reduced by 97.4percent and viable Escherichia coli had been reduced by 99.5 percent ascalculated by comparison with the control cloths.

Example 22 To ml. of water there was added 5 .0 ml. of a solutionprepared by dissolving 10.0 g. of the product obtained in Example 12 in100 ml. of alcohol 3-A and diluting the alcohol solution with water to atotal volume of 1 liter. The solution was heated to 51 C. and a 1.76 g.sample of multifiber cloth was added and agitated at this temperaturefor twenty minutes. The cloth was removed, rinsed for two minutes withcold running tap water and then pressed dry between paper towels. All ofthe fibers contained in the swatch, viz. cellulose acetate,acrylonitrile-vinyl acetate copolymer (Acrilan-Chemstrand), cellulosetriacetate (Arnel-Celanese), cotton, acrylonitrileacrylic esterscopolymer (Creslan-American Cyanamid), poly(ethylene terephthalate)(Dacron-Du Pout), vinyl chloride-acrylonitrile copolymer (Dynel-UnionCarbide), nylon, polyacrylonitrile (Orlon-Du Pont), silk, viscose rayon,wool and acrylonitrile-vinyl acetate copolymer (Zefran-Dow) werebeneficially whitened by this procedure. Exceptionally improved inbrightness were the acrylonitrile-vinyl acetate copolymer, thepolyacrylonitrile, and the acrylonitrile-acrylic esters copolymer.

I claim:

1. A compound of the formula where R R R and R are hydrogen, lower alkylhaving 1 to 4 carbon atoms, lower alkoxy having 1 to 4 carbon atoms, orhalo; Y and Y are lower alkyl having 1 to 6 carbon atoms, hydroxy-loweralkyl having 2 to 6 carbon atoms, 2-hydroxy-3-sulfopropyl,hydroxy-oxaalkyl having 3 to 15 carbon atoms, carboxy-lower alkyl having2 to 6 carbon atoms, cyano-lower alkyl having 2 to 6 carbon atoms,phenyl-lower alkyl having 7 to 11 carbon atoms,

15 allyl or methallyl; Z and Z are lower alkyl having 1 to 6 carbonatoms, hydroxy-lower alkyl having 2 to 6 carbon atoms, carboxy-loweralkyl having 2 to 6 carbon atoms, cyano-lower alkyl having 2 to 6 carbonatoms, phenyllower alkyl having 7 to 11 carbon atoms, allyl, methallyl,or 3-halo-2-propenyl; and An is an anion.

2. A compound, according to claim 1 wherein Y and Y are each allyl; eachof R R R and R is hydrogen; and Z and Z are lower alkyl having 1 to 6carbon atoms, phenyl-lower alkyl having 7 to 11 carbon atoms, allyl or3-halo-2-propenyl.

3. 4,4 stilbenebis(1-allyl-3-methyl-2-benzimidazolium salt), accordingto claim 2 wherein Z and Z are each methyl.

4. 4,4 stilbenebis(1-allyl-3-n-butyl-2-benzimidazolium salt), accordingto claim 2 wherein Z and Z are each nbutyl.

5. 4,4 stilbenebis(1,3-diallyl-2-benzimidazolium salt), according toclaim 2 wherein Z and Z are each allyl.

6. 4,4'-stilbenebis[1-allyl-3-(3-chloro 2 propenyl)-2- benzimidazoliumsalt], according to claim 2 wherein Z and Z are each3-chloro-2-propenyl.

7. 4,4-stilbenebis[l-allyl-3-(4-chlorobenzyl) 2 benzimidazolium salt],according to claim 2 wherein Z and Z are each 4-chlorobenzyl.

8. 4,4'-stilbenebis[1-allyl 3 (4 nitrobenzyl)-2-benzimidazolium salt],according to claim 2 wherein Z and Z are each 4-nitrobenzyl.

9. 4,4'-stilbenebis[1-allyl 3 (dichlorobenzyD-Z-benzimidazolium salt],according to claim 2 wherein Z and Z are each dichlorobenzyl.

10. 4,4 stilbenebis[1-allyl3-(2,3,4,5,6pentachlorobenzyl)-2-benzimidazolium salt], according to claim 2 whereinZ and Z are each 2,3,4,5,6-pentachlorobenzyl.

11. 4,4 stilbenebis[1 allyl-3-(4 dodecylbenZyl)-2- benzimidazoliumsalt], according to claim 2 wherein Z and Z are each 4-dodecylbenzyl.

12. A compound, according to claim 1 wherein Y and Y are eachhydroxy-oxaalkyl having 3 to 15 carbon atoms; each of R R R and R ishydrogen; and Z and Z are allyl or phenyl-lower alkyl having 7 to 11carbon atoms.

13. 4,4'-stilbenebis{3-ally1-1-[2 (2 hydroxyethoxy) ethyl]-2-benzimidazolium salt}, according to claim 12 wherein Z and Z are eachallyl; and Y and Y are each 2- (2-hydroxyethoxy) ethyl.

14. 4,4 stilbenebis{3-(4chlorobenzyl)-1-[2-(2-hydroxyethoxy)ethyl]-2-benzimidazolium salt},according to claim 12 wherein Z and Z are each 4-chlorobenzyl; and Y andY are each 2-(2-hydroxyethoxy)ethyl.

15. A compound, according to claim 1 wherein one of Y and Y ishydroxy-lower alkyl having 2 to 6 carbon atoms and the other ishydroxy-oxaalkyl having 3 to 15 carbon atoms; each of R R R and R ishydrogen; and Z and Z are phenyl-lower alkyl having 7 to 11 carbonatoms.

16. 4-[1-(1-methyl 2 hydroxyethyl)benzimidazol-2- yl]4-{1-[1-methy1 2(2,3 dihydroxypropoxy)ethyl] benzimidazol 2 y1}stilbene N ,Nbis(4-chlorobenzyl salt), according to claim 15 wherein Z and Z are each4-chlorobenzyl; and one of Y and Y is 1-methyl-2-hydroxyethyl and theother is 1-methyl-2-(2,3-dihydroxypropoxy)ethyl.

17. A compound, according to claim 1 wherein each of Y Y Z and Z isphenyl-lower alkyl having7 to 11 carbon atoms; and each of R R R and Ris hydrogen.

18. 4,4'-stilbenebis(1,3-dibenzyl 2 benzimidazolium salt), according toclaim 17 wherein Y Y Z and Z are each benzyl.

19. A COIIIPOUIld, according to claim 1 wherein Y and Y are eachhydroxy-lower alkyl; each of R R R and R is hydrogen; and Z and Z areeach phenyl-lower alkyl.

20. 0 m Bis((2 4'-{1-[2-(2 hydroxyethoxy)ethyl]benzimidazol-2-yl}stilbenyl-4 -1-[2-(2 hydroxyethoxy) ethyl]-3-benzimidazoliurn) )-p-Xylene dichloride.

References Cited UNITED STATES PATENTS 3/1959 Crounse 260-240 6/1958Crounse 260-240 FOREIGN PATENTS 8/1957 Austria 260-240 JOHN D. RANDOLPH,Primary Examiner US. Cl. X.R.

Page 1 of 2 UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OFCORRECTION PATENT NO. 3,583 9 DATED June 8, 1971 lN\/ ENTOR(S) Nathan N.Crounse It is certified that error appears in the above-identifiedpatent and that said Letters Patent are hereby corrected as shown below:

Column 1, line 16,"commitantly"' should read concomltantly Column 1,line +5, the top right of the formula should read Column 2, line 17,"lower alkyl" should read hydroxylower alkyl Column 2, line 60, "anmal"should read animal Column 3, line 71, "deter-gets" should readdetergents column line 314, zimidazo should read (benzimldazol- Column6, Example 1, line 18, delete (corr.

Column 7, Example 10, lines 67-68, "{l-[2-hydroxyethoxy" should read{1-[2-(2-hydroxyethoxy PATENT N0. 3, 583, 98

DATED June 8, 1971 INVENTO 1 Nathan N. Crounse are hereby corrected asshown below:

-- collected Column 8, Example 13, lines Column 11, Example 17, lineread hydroxyethylated Column 13, Example 20, line read quaternary Column1 4, Example 21, line read quaternary [SEAL] A nest:

I RUTH c. mson Alluring Officer Page 2 of 2 UNITED STATES PATENT ANDTRADEMARK OFFICE CERTIFICATE OF CORRECTION It is certified that errorappears in the above-identified patent and'that said Letters PatentColumn 8, Example 10, line 10, "colled" should read 9-50,"(E-hydroxyethyl) benzimidazol-" should read(2-hydroxyethyl)benzimidazoll t, "hydroxyethyl" should 7}, "quarternary"should l8, "quarter-nary" should Signed and Sealed this Seventh Day ofJune 1977 C. MARSHALL DANN Commissioner of Parents and, Trademarks

